JP2023142385A - Oxygen-absorbing laminate - Google Patents

Abstract

To provide an oxygen-absorbing laminate which generates less odor, and is excellent in oxygen gas barrier property, oxygen absorption property, interlayer adhesive strength and heat sealability, and an oxygen-absorbing packaging material which is manufactured from the oxygen-absorbing laminate, suppresses permeation of oxygen gas from outside, absorbs oxygen in a content storage space and thereby suppresses deterioration and odor change due to oxygen of a content, and is excellent in a balance between aroma retention property and content resistance.SOLUTION: An oxygen-absorbing laminate includes at least a printing ink layer, a printing ink component shielding resin layer, an inorganic oxygen barrier layer, an oxygen-absorbing adhesive layer and a sealant layer in this order.SELECTED DRAWING: Figure 1

Description

The present invention generates little odor, suppresses the permeation of oxygen gas from the outside, absorbs oxygen in the packaged contents storage space, suppresses deterioration of the contents due to oxygen, and improves the odor of the contents. An oxygen-absorbing laminate with an excellent balance of change suppression, aroma retention, content resistance, interlayer adhesion strength, heat sealability, amount of odor generated, and oxygen absorption performance, and is suitable for filling packaging. and an oxygen-absorbing packaging material made from the oxygen-absorbing laminate.

Conventionally, packaging methods for suppressing the quality deterioration of the contents of foods, medical products, chemical products, cosmetics, etc. due to oxygen include using packaging materials with high oxygen barrier properties, and using inert gas such as nitrogen gas to seal the contents storage area. However, the performance is insufficient, the packaging cost increases, and the amount of waste increases. Problems have been raised, such as the ability to perform only in environments with moisture and the possibility of accidental ingestion.
Conventional oxygen-absorbing laminates or oxygen-absorbing packaging materials contain oxygen absorbers, which include organic compounds or metal oxygen absorbers such as iron powder; was oxidized and absorbed oxygen in the content storage space.
Further, in many cases, the oxygen absorbing layer containing the oxygen absorbent is placed in a layer closer to the content accommodation space, for example, in a layer adjacent to the sealant layer, in order to increase the oxygen absorption efficiency. There were many.
In addition, when the oxygen absorber is a metal-based oxygen absorber, the above-mentioned inhibition is unlikely to occur, but the coloring of the oxygen absorbing layer by the oxygen absorber becomes intense, and the packaging material is darkly colored, making the contents visible. As a result, the contents could not be inspected using metal detectors, etc., and there were concerns about rust caused by moisture.
Furthermore, Patent Document 1 proposes a packaging material for medical use that has oxygen absorption properties and can be boiled and retorted, but the sealant layer is made of a special highly heat-resistant polyethylene resin that is difficult to obtain. Therefore, there is a problem with versatility.
In addition, in Patent Document 2, a packaging material using a resin that has oxygen absorption properties and generates little odor has been developed, but this resin is insoluble in polar solvents and does not have active hydrogen groups. Since it is dodecene, it is difficult to apply it as an adhesive raw material for packaging materials made of laminates.
Patent Document 3 proposes a laminating adhesive made of a resin using methyltetrahydrophthalic acid as a raw material having oxygen absorbing properties, but it has the disadvantage of low oxygen absorbing properties and instability.
Patent Document 4 discloses oxygen absorption of a thermoplastic resin having a repeating unit consisting of a saturated five-membered ring having a substituent containing a carbon-carbon double bond and a -CH=CH- group connecting the five-membered rings. However, it has drawbacks such as poor solubility in solvents, which makes it difficult to use, and a strong odor.

Patent No. 6403999 Patent No. 5873770 Patent No. 5671816 Patent No. 6505699

The objects of the present invention are to have low odor generation, oxygen gas barrier properties, oxygen absorption properties, interlayer adhesive strength,
An oxygen-absorbing laminate with excellent heat-sealing properties, and an oxygen-absorbing laminate made from the oxygen-absorbing laminate, suppressing the permeation of oxygen gas from the outside and absorbing oxygen in the content storage space, thereby reducing oxygen in the contents. It is an object of the present invention to provide an oxygen-absorbing packaging material that suppresses deterioration and change in odor and taste due to oxygen and has an excellent balance between aroma retention and content resistance.

Therefore, in order to solve the above-mentioned problems, the present inventors have developed a system that includes at least a printing ink layer, a printing ink component shielding resin layer, an inorganic oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer. It has been found that an oxygen-absorbing laminate containing the following compounds can solve the above problems.
That is, the present invention is characterized by the following points.

1. An oxygen-absorbing laminate comprising at least a printing ink layer, a printing ink component shielding resin layer, an inorganic oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer in this order,
The printing ink layer contains a metal oxide pigment,
The printing ink component shielding resin layer contains one or more selected from the group consisting of nylon resin, polyolefin resin, and polyester resin,
The inorganic oxygen barrier layer contains a metal or a metal oxide,
The oxygen-absorbing adhesive layer is a layer formed from an oxygen-absorbing adhesive composition,
The oxygen-absorbing adhesive composition contains at least an oxygen-absorbing compound and an oxidation promoting catalyst,
The oxygen-absorbing compound has one or more unsaturated five-membered rings,
Any bond between the five carbon atoms constituting the unsaturated five-membered ring is a carbon-carbon double bond,
A monovalent and/or divalent or more valent electron-donating organic group 1 is bonded to the unsaturated five-membered ring,
When there is one unsaturated five-membered ring, the five-membered ring or the organic group 1 is a functional group having an active hydrogen, or the active hydrogen of the functional group having an active hydrogen is a monovalent organic group 2. has a substituted group,
When there are two or more unsaturated five-membered rings, each unsaturated five-membered ring has a divalent or higher valence that replaces the active hydrogen of the active hydrogen group on each five-membered ring or the organic group 1. An oxygen-absorbing laminate characterized by being bonded via an organic group 2.
2. The structure of the unsaturated five-membered ring or the structure consisting of the unsaturated five-membered ring and the organic group 1 is one or two selected from the group consisting of cyclopentadiene, dicyclopentadiene, norbornene, and derivatives thereof. The oxygen-absorbing laminate described in 1 above, which is derived from the above.
3. 3. The oxygen-absorbing laminate described in 1 or 2 above, wherein the organic group 2 includes a structural part derived from an isocyanate compound or an isocyanate compound and a hydroxyl group-containing compound.
4. Item 3 above, wherein the isocyanate compound is one or more selected from the group consisting of xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and derivatives thereof. oxygen-absorbing laminate.
5. The hydroxyl group-containing compound is selected from the group consisting of polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, phenoxy resins, and urethane chain-elongated polyols thereof. 5. The oxygen-absorbing laminate described in 3 or 4 above, characterized in that the oxygen-absorbing laminate comprises one or more types.
6. 6. The oxygen-absorbing laminate according to any one of 1 to 5 above, wherein the organic group 2 does not have a crosslinkable functional group.
7. The organic group 2 has one or more crosslinkable functional groups,
6. The oxygen-absorbing laminate according to any one of 1 to 5 above, wherein the crosslinkable functional group is a hydroxyl group and/or an isocyanate group.

（式中、ａ～ｅは各々１以上の数であり、Ｒ¹、Ｒ²、Ｒ³の各々は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含み、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。）
９． 前記酸素吸収性化合物が、下記式（５）で示される化合物を含有することを特徴とする、上記１～５の何れかに記載の酸素吸収性積層体。

（式中、ｆは０以上の数であり、Ｒ⁴とＲ⁵の各々は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含む有機基であり、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） 8. As described in any one of 1 to 5 above, the oxygen-absorbing compound contains one or more selected from the group consisting of compounds represented by the following formulas (1) to (4). oxygen-absorbing laminate.

(In the formula, each of a to e is a number of 1 or more, each of R ¹ , R ² , and R ³ is an organic group having 1 or more carbon atoms and includes at least an alkylene and/or phenylene structure, and further, One or more selected from the group consisting of polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylic acid ester polyols, phenoxy resins, and these urethane chain extension polyols. (Can include derived structures.)
9. 6. The oxygen-absorbing laminate according to any one of 1 to 5 above, wherein the oxygen-absorbing compound contains a compound represented by the following formula (5).

(In the formula, f is a number of 0 or more, each of R ⁴ and R ⁵ is an organic group having 1 or more carbon atoms, an organic group containing at least an alkylene and/or phenylene structure, and a polyvalent Derived from one or more selected from the group consisting of alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, phenoxy resins, and these urethane chain-extended polyols structure.)

10. 10. The oxygen-absorbing laminate according to any one of 1 to 9 above, wherein the oxidation-promoting catalyst is a peroxide or a compound containing a cation made of a transition metal.
11. The compound containing a cation made of a transition metal is a metal soap made of a transition metal compound capable of releasing a cation or a complex made of a transition metal, and an anion or a ligand made of a fatty acid. The oxygen-absorbing laminate according to any one of 1 to 10. 12. The oxygen-absorbing adhesive composition further contains a modifier,
12. The oxygen-absorbing laminate according to any one of items 1 to 11 above, wherein the modifier contains an isocyanate compound and/or a hydroxyl group-containing compound.
13. Item 12 above, wherein the isocyanate compound is one or more selected from the group consisting of xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and derivatives thereof. oxygen-absorbing laminate.
14. The hydroxyl group-containing compound is characterized in that it contains one or more selected from the group consisting of polyester polyols, poly(meth)acrylate polyols, polyalkylene ether diols, and these urethane chain-extended polyols. 14. The oxygen-absorbing laminate described in 12 or 13 above.
15. An oxygen-absorbing packaging material produced using the oxygen-absorbing laminate according to any one of items 1 to 14 above.

According to the present invention, there is provided an oxygen-absorbing laminate that generates little odor and has excellent oxygen gas barrier properties, oxygen absorption properties, interlayer adhesion strength, and heat-sealing properties, and an oxygen-absorbing laminate that is produced from the oxygen-absorbing laminate and that is free from external oxygen. By suppressing gas permeation and absorbing oxygen in the content storage space, it suppresses deterioration of the content due to oxygen, and achieves a balance between suppressing changes in the odor of the content, aroma retention, and content resistance. An excellent oxygen-absorbing packaging material can be obtained.
Less odor generated means less change in odor and taste of the contents.
The oxygen-absorbing laminate and oxygen-absorbing packaging material of the present invention shorten the packaging process, reduce costs, and reduce the weight of oxygen-absorbing packaging containers. Since packaging is not required, it is possible to eliminate the accidental ingestion of the oxygen absorber and reduce the amount of waste made of the oxygen absorber.

FIG. 1 is a cross-sectional view showing an example of the layer structure of the oxygen-absorbing laminate of the present invention.

The above invention will be explained in more detail below. The explanation of the constituent elements described below is an example of the embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist thereof.
Note that in the present invention, the terms "film" and "sheet" have the same meaning.

<<Oxygen absorbing laminate>>
The oxygen-absorbing laminate of the present invention has a layer structure including at least a printing ink layer, a printing ink component shielding resin layer, an inorganic oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer in this order. have.
The printing ink layer may be a surface layer of the oxygen-absorbing laminate, or another layer may be laminated on the printing ink layer.
When packaging using the oxygen-absorbing laminate of the present invention, the sealant layer is heat-sealed, and the inorganic oxygen barrier layer is positioned outside the oxygen-absorbing adhesive layer.
By positioning the inorganic oxygen barrier layer outside the oxygen-absorbing adhesive layer, oxygen is prevented from permeating the packaging material from the outside, and the oxygen-absorbing adhesive layer absorbs oxygen inside the packaging. The efficiency of reducing oxygen concentration can be increased.
A printing ink component shielding resin layer between which printing ink components such as metal oxide pigments contained in the printing ink layer, especially titanium oxide contained in white ink, migrates to the oxygen-absorbing adhesive layer. This suppresses the decrease in oxygen absorption efficiency of the oxygen-absorbing adhesive layer.
Furthermore, the oxygen-absorbing adhesive layer in the present invention is a layer formed from an oxygen-absorbing adhesive composition containing an oxygen-absorbing compound that is an organic compound and an oxidation promoting catalyst, Since the layer does not contain an oxygen absorber, there is no dark coloring caused by metal oxygen absorbers, and if an inorganic oxygen barrier layer made of a transparent vapor-deposited film made of a specific metal oxide such as alumina is used, packaging The contents inside the body can be visually confirmed, the contents can be inspected using a metal detector, etc., and there is no concern that rust will develop due to moisture.
The sealant layer contains a heat-sealable resin, but if the oxygen-absorbing laminate is exposed to high temperatures, use a grade of the above resin with high heat resistance and oxidation resistance to improve heat resistance and oxidation resistance. It is preferable to increase the deteriorability.
For example, it is preferable that the softening point of the sealant layer is 120° C. or higher.

The oxygen-absorbing laminate can further include various functional layers having various functions, if necessary. Examples of the functional layer include an auxiliary barrier layer, a fragrance layer, a light shielding layer, and a reinforcing layer.
Furthermore, a general-purpose adhesive layer can be included between each of the above layers or within each layer to improve interlayer adhesion.

[Contents]
In the above, the contents include coffee beans, tea leaves, cheese, snacks, rice crackers, fresh and semi-fresh sweets, fruits, nuts, vegetables, fruits, fish and meat products, paste products, dried fish, smoked foods, tsukudani, raw rice, Foods such as rice, rice cakes, infant foods, jams, mayonnaise, ketchup, edible oil, dressings, sauces, spices, dairy products, pet food, and beverages such as beer, wine, fruit juice, green tea, coffee, etc. Examples include, but are not limited to, pharmaceuticals, cosmetics, shampoos and conditioners, detergents, metal parts, and electronic parts.

<About each layer constituting the oxygen-absorbing laminate>

≪Printing ink layer≫
The printing ink layer is used for decoration, display of contents, display of expiration date, display of manufacturer, seller, etc., and for imparting aesthetic appearance, such as letters, numbers, figures, symbols, patterns, etc. It visually shows a design pattern such as a pattern, and can form a desired design pattern.
The printing ink layer shall be formed on the surface of the printing ink component shielding resin layer of the base material layer on the opposite side from the inorganic oxygen barrier layer and the oxygen-absorbing adhesive layer by a printing method such as a gravure printing method or a flexographic printing method. is preferred. The printing ink layer may be provided on the entire surface of the printing surface, or may be provided on a part of the surface.
The printing ink layer may be only a solid layer, or may be composed of a printing ink pattern layer and a printing ink solid layer as shown in FIG.
The printing ink layer can contain various pigments, for example, metal oxide pigments.
Metal oxide pigments usually tend to inhibit the oxygen absorption performance of organic oxygen-absorbing compounds contained in the oxygen-absorbing layer, but the oxygen-absorbing laminate of the present invention has a printing ink component shielding resin layer. By having it, you can use it without any problems.
Specific examples of metal oxide pigments include titanium oxide white pigments.
The thickness of the printing ink layer can be set appropriately by those skilled in the art, but in order to give the printing ink layer appropriate durability, it is preferably 0.5g/mm ² to 5g/mm ² , and 1g/mm 2 to 5g/mm 2 . It is more preferably from mm ² to 4 g/mm ² , even more preferably from 2 g/mm ² to 3 g/mm ² .

≪Printing ink component shielding resin layer≫
The printing ink component shielding resin layer suppresses the migration of printing ink components contained in the printing ink layer, especially titanium oxide contained in white ink, to the oxygen-absorbing adhesive layer, and reduces oxygen absorption in the oxygen-absorbing adhesive layer. This is a layer that suppresses a decrease in efficiency.
The printing ink component shielding resin layer can also serve as a base material layer. By also serving as a base material layer, it becomes possible to reduce the total number of constituent layers of the oxygen-absorbing laminate and to reduce the overall thickness.
The material for the printing ink component shielding resin layer has excellent mechanical, physical, chemical, and other properties, and in particular, is a commonly known material that is strong, tough, and heat resistant. A publicly available resin film can be used. Furthermore, various paper base materials can be used in combination.
The printing ink component shielding resin layer may be composed of one layer, or may be composed of two or more layers having the same or different compositions and laminated by any laminating means.
The thickness of the printing ink component shielding resin layer is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and 15 μm to 100 μm, for the purpose of providing a sufficient printing ink component shielding effect and appropriate strength and stiffness to the laminate. More preferably, the thickness is 25 μm.

The printing ink component shielding resin layer preferably has a density of 0.9 to 1.8 g/cm ³ . If the density is smaller than the above range, the strength is likely to be impaired, and if the density is larger than the above range, the flexibility is likely to be reduced.

The printing ink component shielding resin layer is preferably a layer made of a resin film.
Specific resin films include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefin resins such as polypropylene, polyamide resins such as nylon, polyaramid resins, polycarbonate resins, polyacetal resins, and fluorine resins. Examples include resin films made using tough thermoplastic resins such as thermoplastic resins and other tough thermoplastic resins.
The above-mentioned resin film can be either an unstretched film or a uniaxially or biaxially stretched stretched film.
Among the above, biaxially stretched PET film and biaxially stretched nylon film are preferably used.

The paper base material can be imparted with shapeability, bending resistance, rigidity, etc., such as bleached or unbleached paper base material for paper layers with strong size properties, pure white roll paper, kraft paper, etc. Paper base materials such as paperboard, coated paper, processed paper, milk base paper, and others can be used.
The paper base material preferably has a basis weight of about 30 g/m ² to 600 g/m ² , more preferably about 50 g/m ² to 450 g/m ² .

The resin film used for the printing ink component shielding resin layer has processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold releasability, flame retardancy, Plastics such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. for the purpose of improving and modifying anti-fungal properties, electrical properties, strength, etc. Compounding agents, additives, etc. can be added, and the amount thereof can be arbitrarily added depending on the purpose within a range that does not adversely affect other performances.
The printing ink component shielding resin layer can be laminated with other layers via an adhesive layer. Furthermore, if necessary, in order to strengthen the adhesive strength between the base material layer and the adhesive layer, the surface of the base material layer in contact with the adhesive may be treated with corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, etc. It is also possible to perform a physical surface treatment such as surface treatment, sandblasting, etc., or a chemical surface treatment such as an oxidation treatment using chemicals in advance.

≪Inorganic oxygen barrier layer≫
The inorganic oxygen barrier layer is a layer that suppresses permeation of oxygen from the outside of the package to the content storage section inside the package in a package made using an oxygen-absorbing laminate.
In an oxygen-absorbing pouch made using an oxygen-absorbing laminate, the inorganic oxygen barrier layer is located outside the oxygen-absorbing adhesive layer, which suppresses oxygen from entering from outside the package. , the oxygen-absorbing adhesive layer absorbs oxygen in the contents storage section inside the package, thereby increasing the effect of lowering the oxygen concentration.
The inorganic oxygen barrier layer may include various oxygen barrier materials such as inorganic vapor deposited films and metal foils containing one or more selected from the group consisting of metals, metal oxides, metal nitrides, and metal carbides. can be used.
Furthermore, it may be an oxygen barrier material that has barrier properties not only against oxygen, but also against water vapor, etc., light shielding properties against sunlight, etc., aroma retention properties against contents, and the like. Alternatively, barrier materials having these barrier properties may be used together.

Among the above, the metal vapor deposited film or the metal oxide vapor deposit film deposited on the resin film constituting the printing ink component shielding resin layer has particularly excellent barrier properties against oxygen gas, water vapor, light shielding properties, aroma retention properties, etc. This is preferable because it is easy to carry out and has the advantage of being environmentally friendly in terms of container disposal.
Furthermore, in the case of a vapor-deposited film made of a specific metal oxide, such as alumina (aluminum oxide), the inorganic oxygen barrier layer and the laminate can be made transparent, making it possible to visually check the contents inside the package. Therefore, the contents can be inspected using a metal detector, etc., and there is no concern about rust caused by moisture.
A specific example of metal foil is aluminum foil. The thickness of the aluminum foil is preferably 5 μm to 30 μm.

Specific examples of the metal elements constituting the above-mentioned inorganic compounds such as metals, metal oxides, metal nitrides, and metal carbides include aluminum (Al), silicon (Si), magnesium (Mg), and calcium (Ca). , potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), zinc (Zn), vanadium (V) , barium (Ba), chromium (Cr), and the like.

Specific examples of inorganic compounds include indium _tin oxide (ITO), _SiO Also included are complex inorganic compounds such as membranes.
Specific examples of the inorganic compound of the inorganic vapor deposition layer include silica (silicon oxide), alumina (aluminum oxide), silicon nitride, silicon carbide, and the like. Among these, silica and alumina are preferred.

The average composition of an inorganic compound is expressed as MO _x , MO _x C _y , such as SiO _x , AlO _x , SiO _x C _y (wherein, M represents a metal element, and the values of x and y The range varies depending on the metal element.) In the case of metal oxides, the value of X ranges from 0 to 2 for silicon, 0 to 1.5 for aluminum, 0 to 1 for magnesium, 0 to 1 for calcium, and 0 to 0. for potassium. 5. Tin is 0 to 2, sodium is 0 to 0.5, boron is
0 to 1, 5 for titanium, 0 to 2 for lead, 0 to 1 for zirconium, and 0 to 1.5 for yttrium.
In the above MO _X , when x=0, it is metal and not transparent, and the upper limit of the range of x is the value when completely oxidized.
In the present invention, silicon oxide and aluminum oxide are preferably used, and silicon oxide has x in the range of 1.0 to 2.0, and aluminum oxide has x in the range of 0.5 to 1.5. be able to.
The inorganic oxygen barrier layer may be formed of one type of these barrier materials, or may be used in combination of two or more types, or may be used as a mixture of two or more types. Further, it may be composed of one layer, or may be composed of multiple layers having the same or different compositions, and in the case of multiple layers, they do not need to be stacked adjacently.

The resin film that supports the inorganic oxygen barrier layer has a vapor-deposited layer of an inorganic compound, so it has excellent mechanical, physical, chemical, and other properties, and is particularly strong and tough. It is preferable to use a resin film that is also heat resistant.
The resin film supporting the above-mentioned inorganic oxygen barrier layer may be a resin film constituting a printing ink component shielding resin layer, or may be another resin film.
When adhering an inorganic oxygen barrier layer to a resin film, it can be adhered and laminated via an oxygen-absorbing adhesive composition or a general-purpose adhesive layer.
When laminating the resin film with an inorganic vapor-deposited layer, the surface of the resin film with an inorganic vapor-deposited layer may be subjected to corona discharge treatment, ozone treatment, etc., if necessary, in order to strengthen the adhesive strength with other layers. The surface treatment layer can also be formed by previously performing physical surface treatment such as plasma treatment, glow discharge treatment, sandblasting treatment, etc., or chemical surface treatment such as oxidation treatment using chemicals.

Specifically, in the present invention, examples of the resin film supporting the inorganic vapor deposited layer include polyester resin films such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and polyamide resins such as various nylons. Polyolefin films such as films, polyethylene resins, polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), polybutene resin films, Polyvinyl chloride resin, polycarbonate resin, polyimide resin, polyamideimide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, cellulose resin , poly(meth)acrylic resin, polyvinylidene chloride film, acetal resin film, fluorine resin, and others.
Among the above resins, it is particularly preferable to use a film of polypropylene resin, polyester resin, or polyamide resin.

As the resin film that supports the above-mentioned inorganic vapor deposited layer, an oxygen barrier resin coating film or an oxygen barrier resin film made of an oxygen barrier resin can be used, and at the same time, it has gas barrier properties against water vapor, aroma retention, etc. It can also be demonstrated.
Examples of oxygen barrier resins include polyvinylidene chloride resins (PVDC), polyester resins, polyamide resins (especially aromatic polyamides such as nylon MXD6), and ethylene-vinyl acetate copolymers (vinyl acetate contains approximately 79 wt%). Films of resins with rich gas barrier properties such as ethylene-vinyl alcohol copolymer (EVOH) with an ethylene content of 25 mol % to 50 mol %, polyvinyl alcohol, polyacrylonitrile, etc., which are completely saponified of 92 wt %), or Coating membranes can be used.
The thickness of the resin film supporting the inorganic vapor deposition layer is arbitrary, but is preferably 0.5 μm to 300 μm, more preferably 1 μm to 100 μm.

Methods for forming the inorganic vapor deposition layer include, for example, physical vapor deposition methods (PVD methods) such as vacuum evaporation methods, sputtering methods, ion plating methods, cluster ion beam methods, etc., using the above-mentioned inorganic compounds as raw materials. ), or inorganic vapor deposition on a resin film using a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. layers can be formed.

More specifically, in the above-mentioned PVD method, for example, a winding type vapor deposition machine is used, and the resin film released from the unwinding roll is put into the vapor deposition chamber in a vacuum chamber, and here, The vapor deposition source heated in the crucible is evaporated, and if necessary, an inorganic vapor deposition layer is formed on the resin film on the cooled coating drum through a mask while blowing out oxygen etc. from the oxygen outlet. Then, by winding up the resin film on which the inorganic vapor deposited layer is formed onto a take-up roll, the resin film with the inorganic vapor deposited layer according to the present invention can be manufactured.

On the other hand, in the above-mentioned CVD method, a monomer, such as a monomer supplied from a vapor deposition raw material volatilization supply device, is applied to the surface of the resin film fed out from an unwinding roll disposed in the vapor deposition chamber, while cooling in the vapor deposition chamber and on the circumferential surface of the electrode drum. A resin film on which a deposited layer of silicon oxide is formed by plasma can be produced by introducing a mixed gas consisting of an organic silicon compound, oxygen gas, inert gas, etc. as a gas.

In the above, the thickness of the inorganic deposited layer is preferably 30 Å to 3000 Å, more preferably 40 Å to 2500 Å, and even more preferably 50 Å to 2000 Å, in order to obtain sufficient oxygen barrier properties.
More specifically, in the above-mentioned PVD method, the thickness of the inorganic vapor deposited layer made of aluminum oxide is preferably about 30 Å to 1000 Å, more preferably about 50 Å to 500 Å.
Further, in the above CVD method, the thickness of the inorganic vapor deposited layer made of silicon oxide is preferably 30 Å to 3000 Å, more preferably 100 Å to 300 Å.
In addition, if the thickness of the inorganic vapor deposited layer exceeds the above range, cracks etc. will easily occur in the inorganic vapor deposited layer, and there is a risk that the barrier property will decrease, and the material cost will increase, so it is preferable. do not have. Further, if it is less than the above range, it is not preferable because it tends to be difficult to exhibit sufficient oxygen barrier properties.

In addition, the resin film with an inorganic vapor deposition layer preferably has an acidity permeability of 3.0 cc/m ² ·atm · day or less when measured in accordance with the JIS K7126 method in an environment of a temperature of 23°C and a humidity of 90% RH. It is more preferably 2.0 cc/m ² ·atm · day or less, and even more preferably 1.0 cc/m ² ·atm · day or less. If the oxygen permeability satisfies the above-mentioned numerical range, it is possible to sufficiently suppress the intrusion of oxygen from the outside of the package into the content storage section inside the package.
Further, the resin film with an inorganic vapor deposited layer preferably has a water vapor permeability of 3.0 g/m ² ·day or less when measured in accordance with JIS K7129 method in an environment of a temperature of 40° C. and a humidity of 100% RH, More preferably, it is 2.0 g/m ² ·day or less, and still more preferably 1.5 g/m ² ·day or less. If the water vapor permeability satisfies the above numerical range, it is possible to sufficiently suppress the intrusion of water vapor from the outside of the package into the content storage section inside the package.

When forming the above-mentioned inorganic vapor deposited layer, the surface of the resin film to be vapor deposited is cleaned by pretreatment such as SiO _x plasma, and polar groups and free radicals are generated on the surface, so that the inorganic vapor deposited layer Close adhesion to the film can be improved.
Furthermore, when two or more inorganic vapor deposition layers are successively laminated using a plasma chemical vapor deposition apparatus consisting of at least two or more film forming chambers, each layer must be vapor-deposited to have high gas barrier properties. Because of this, it is possible to obtain gas barrier properties that are even higher than that of a single layer. Furthermore, by continuous vapor deposition without being exposed to the atmosphere, foreign matter, dust, etc. that can cause cracks are removed between the inorganic vapor-deposited layers. Contamination can be prevented, and the gas barrier properties are improved.
Furthermore, if the composition of each vapor deposited layer is different, since the inorganic vapor deposited layers are different discontinuous layers, the permeation of oxygen gas, water vapor, etc. can be suppressed more efficiently.

≪Oxygen-absorbing adhesive layer≫
The oxygen-absorbing adhesive layer is a layer formed using an oxygen-absorbing adhesive composition, and is a layer that absorbs oxygen.

《Oxygen-absorbing adhesive composition》
The oxygen-absorbing adhesive composition of the present invention contains at least an oxygen-absorbing compound and an oxidation-promoting catalyst.
The oxygen-absorbing compound contained may be one type or two or more types, and the oxidation promoting catalyst contained may be one type or two or more types.
The oxygen-absorbing adhesive composition can further contain a modifier, a diluting solvent, various additives, and the like, if necessary.

The oxygen-absorbing adhesive composition may be prepared by adding an oxygen-absorbing compound to an existing adhesive composition, or by using the oxygen-absorbing compound as a resin component.
Here, the existing oxygen-absorbing adhesive composition may be a one-component oxygen-absorbing adhesive composition or a two-component oxygen-absorbing adhesive composition.
The oxygen absorbing adhesive composition and/or the existing adhesive compositions described above may be curable or non-curable. In the case of curability, it may be thermosetting, photocurable, electron beam curable, or the like.
The oxygen-absorbing compound may or may not react with components contained in existing adhesive compositions. Further, the oxygen-absorbing compounds may react with each other.
Depending on the presence or absence of the above reactions and the type of reaction, the oxygen-absorbing compound may be one that does not have a functional group, one that has a (co)polymerizable functional group, or one that has a functional group that can react as a main agent or a curing agent. However, one type or two or more types can be selected and used.

Specifically, for example, an oxygen absorbing compound without a functional group and/or an oxygen absorbing compound having a functional group is added to a two-component urethane adhesive composition containing an isocyanate compound and a hydroxyl group-containing compound. Compounds can be added. In this case, the functional group is preferably an isocyanate group and/or a hydroxyl group.
For example, the combination of the main ingredient and curing agent of the oxygen-absorbing adhesive composition may be a combination of an isocyanate-based compound and an oxygen-absorbing compound having a hydroxyl group, or a combination of a hydroxyl-containing compound and an oxygen-absorbing compound having an isocyanate group. An oxygen-absorbing adhesive composition can be prepared by combining a hydroxyl group-containing oxygen-absorbing compound with an isocyanate group-containing oxygen-absorbing compound.
The oxygen-absorbing adhesive composition is preferably a urethane-based oxygen-absorbing adhesive composition.

The solid content in the oxygen-absorbing adhesive composition is not particularly limited, but is preferably 20% by mass or more and 100% by mass or less.

The content of the oxygen-absorbing compound in the solid content excluding the oxidation-promoting catalyst in the oxygen-absorbing adhesive composition is preferably 40% by mass or more and 100% by mass or less. If it is less than the above range, there is a risk that oxygen absorption will be insufficient. The case of 100% by mass means that the oxygen-absorbing compound can be used as a resin component of the adhesive composition, and has sufficient adhesive properties alone or has a functional group that can be cured alone. In other cases, an oxygen-absorbing compound having a functional group serving as a main ingredient and an oxygen-absorbing compound having a functional group serving as a curing agent are used in combination.

The content of the oxidation promoting catalyst in the oxygen-absorbing adhesive composition is preferably 10 ppm or more and 6000 ppm or less based on the oxygen-absorbing compound.
If the content is less than the above range, oxygen absorption may become insufficient, and if the content is more than the above range, oxygen absorption tends to become unstable, making it difficult to produce oxygen absorbing packaging containers. The oxygen absorbency is consumed beforehand, and there is a risk that the effect of suppressing deterioration due to oxygen after the production of an oxygen-absorbing packaging container may be impaired.

[Oxygen absorbing compound]
The oxygen-absorbing compound in the present invention has oxygen-absorbing properties, generates little odor, and can be used alone or mixed with a resin or resin composition.
The oxygen-absorbing compound of the present invention is an unsaturated five-membered ring-containing compound having one or more unsaturated five-membered rings, in which Any of the bonds is a carbon-carbon double bond, and a monovalent and/or divalent or more valent electron-donating organic group 1 is bonded to the unsaturated five-membered ring.
When there is one unsaturated five-membered ring, the five-membered ring or the organic group 1 is a functional group having an active hydrogen, or the active hydrogen of the functional group having an active hydrogen is a monovalent organic group 2. When the unsaturated five-membered rings have two or more substituted groups, the unsaturated five-membered rings substitute the active hydrogen of the active hydrogen group on each of the organic groups 1. It is bonded via an organic group 2 having a valence or higher.
When there are two or more unsaturated five-membered rings in one molecule, the active hydrogen of the functional group having active hydrogen on each five-membered ring or organic group 1 is , are bonded via a structure substituted with a divalent or higher organic group 2.
Each of the unsaturated five-membered ring, organic group 1, and organic group 2 present in one molecule may be one type or two or more types, and the number may be one or two or more. Further, the number of organic groups 1 bonded to one unsaturated five-membered ring may be one or two or more. Furthermore, the oxygen-absorbing compound is a mixture of molecules having two or more types of structures in which each type and number of unsaturated five-membered rings, organic groups 1, and organic groups 2 present in one molecule are different, as described above. It may be.

When the organic group 1 donates electrons to the unsaturated five-membered ring, the electron density of the carbon-carbon double bond portion of the unsaturated five-membered ring increases, and the reactivity with oxygen increases, resulting in oxygen absorption. increases.
It is preferable that no electron-withdrawing group is bonded to the unsaturated five-membered ring. Due to the bonding of the electron-withdrawing group, the electron density of the carbon-carbon double bond portion of the unsaturated five-membered ring is lowered, the reactivity with oxygen is lowered, and the oxygen absorption property is lowered.
Specific molecular structures of oxygen-absorbing compounds include, for example, one in which one unsaturated five-membered ring and a monovalent or divalent organic group 1 are bonded, one unsaturated five-membered ring and A monovalent or divalent organic group 1 and a monovalent organic group 2 are bonded in this order, and two unsaturated five-membered rings are bonded via a divalent organic group 1 and a divalent organic group 2. Examples include those in which the three unsaturated five-membered rings are bonded via a divalent organic group 1 and a trivalent organic group 2, and the like.

Further, the oxygen-absorbing compound does not need to have a crosslinkable functional group, but can have one.
The crosslinkable functional group may be a functional group possessed by the compound from which the organic group 2 is derived, or may be a functional group added by chemical modification.
Because the oxygen-absorbing compound has a crosslinkable functional group, when the oxygen-absorbing compound is mixed with a resin or a resin composition, the oxygen-absorbing compound is not compatible with the resin or the resin composition. The resin or the resin composition may become a part of the crosslinked structure of the resin or the resin composition, and become difficult to bleed from the resin, the resin composition, or the cured product of the resin composition. The content of oxygen-absorbing compounds in the product can be increased.
Specific examples of the crosslinkable functional group include aliphatic hydroxyl groups, aromatic hydroxyl groups, isocyanate groups, amino groups, epoxy groups, (meth)acrylic groups, and the like. Among these, isocyanate groups and aliphatic hydroxyl groups are preferred.
When the oxygen-absorbing compound has a crosslinkable functional group, the number of crosslinkable functional groups in one molecule is preferably one or more. Further, the number of crosslinkable functional groups contained in one molecule may be one or two or more.
The functional group equivalent of the crosslinkable functional group is not particularly limited, but is preferably from 500 to 20,000, more preferably from 1,000 to 15,000, even more preferably from 1,500 to 10,000.

The number average molecular weight of the oxygen-absorbing compound is preferably 100 to 10,000, more preferably 200 to 5,000, even more preferably 300 to 2,500. When the number average molecular weight is smaller than the above range, precipitation is likely to occur when mixed with a resin or resin composition. If the number average molecular weight is larger than the above range, when mixed with a resin or resin composition, the viscosity of the mixture increases, making it necessary to contain a large amount of diluting solvent, making it difficult to obtain a thick film or layer, Coating suitability tends to deteriorate.

Further, the oxygen absorption effect of the oxygen-absorbing compound of the present invention can be promoted by heating or adding a catalyst.

(unsaturated five-membered ring)
The unsaturated five-membered ring possessed by the oxygen-absorbing compound has a carbon-carbon double bond within the unsaturated five-membered ring. Here, the carbon-carbon double bond is any bond between five carbon atoms constituting an unsaturated five-membered ring, and there may be one bond within one unsaturated five-membered ring, There may be two pieces.
The oxygen-absorbing compound exhibits oxygen-absorbing properties when the carbon-carbon double bond reacts with oxygen molecules in the air and takes in the oxygen molecules.
Examples of compounds from which the unsaturated five-membered ring or the unsaturated five-membered ring to which the electron-donating organic group 1 is bonded include cyclopentadiene, dicyclopentadiene, norbornene, and derivatives thereof. can be mentioned. The oxygen-absorbing compound can have an unsaturated five-membered ring derived from one or more types selected from the group consisting of these.
The concentration of unsaturated five-membered rings in the oxygen-absorbing compound is not particularly limited, but is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less. If it is lower than the above range, the oxygen absorbency tends to be insufficient, it is difficult to obtain an oxygen absorbing compound higher than the above range, and the balance with various physical properties tends to be poor.

(Electron-donating organic group 1)
Specific examples of the organic group 1 include an alkyl group, an alkylene group, a cyclic alkylene group, and the like. Among these, a cyclic alkylene group is preferred, and one that forms an aliphatic bicyclic alkylene group together with the unsaturated five-membered ring is more preferred.
Specific examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. Among these, a cyclopentylene group is more preferred.

(Electron-withdrawing organic group)
Specific examples of the electron-withdrawing group include phenyl group, phenylene group, carbonyl group, halogen, and the like.
Indene and coumaron, in which only these electron-withdrawing groups are bonded to an unsaturated five-membered ring, the electron density of the carbon-carbon double bond portion of the unsaturated five-membered ring becomes low, and the reactivity with oxygen decreases. However, oxygen absorption is low.

(Functional group having active hydrogen)
A functional group having active hydrogen is chemically reactive.
Specific examples of functional groups having active hydrogen include primary amino groups, secondary amino groups, aliphatic hydroxyl groups, aromatic hydroxyl groups, imino groups, carboxyl groups, urethane groups, and urea groups. Amino groups, secondary amino groups, aliphatic hydroxyl groups, and aromatic hydroxyl groups are preferred, and aliphatic hydroxyl groups are more preferred.

(Organic group 2)
Organic group 2 is a monovalent and/or divalent or more valent group that substitutes the active hydrogen of a functional group having active hydrogen on the five-membered ring or organic group 1 and is bonded to the five-membered ring or organic group 1. It is the basis of
When there are two or more unsaturated five-membered rings in one molecule, the unsaturated five-membered rings have a structure in which the active hydrogen of a functional group having active hydrogen is substituted with an organic group 2 having a valence of 2 or more. are connected via.
As a specific example, for example, a functional group having active hydrogen on organic group 1 reacts with an isocyanate group of an isocyanate compound having a structural part from which organic group 2 is derived, and the active hydrogen is converted to organic group 2. It can be substituted and bonded by a urethane group.
Due to the bonding of the organic group 2, the oxygen-absorbing compound can have two or more unsaturated five-membered rings in one molecule, and can further be mixed with a resin or a resin composition to prepare a mixture. The compatibility, dispersibility, and reactivity can be improved. Furthermore, the mixture and the cured product of the mixture can be adjusted to be soft.

The organic group 2 may be an aliphatic group, an aromatic group, or may have both an aliphatic group and an aromatic group.
The number of organic groups 2 present in one molecule of the oxygen-absorbing compound may be one or two or more.
The organic group 2 is preferably a group containing a structural part derived from an isocyanate compound and/or a hydroxyl group-containing compound. Here, the structural part derived from an isocyanate compound and/or a hydroxyl group-containing compound includes a structural part derived from a reaction product of an isocyanate compound and a hydroxyl group-containing compound.

(Isocyanate compound)
Examples of the isocyanate compounds from which the above organic group 2 is derived include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, xylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, diphenyl ether diisocyanate, water Examples include doped diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, trimethylolpropane adducts thereof, biuret forms, allophanate forms, isocyanurate forms (trimers), and various derivatives thereof. Among these, biurette forms of toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate are preferred.
In the present invention, one or more selected from the group consisting of these isocyanate compounds can be used as the origin of the above-mentioned monovalent and/or divalent or more hydrocarbon group structure. When two or more types are used, two types may be used in the same molecule of the oxygen-absorbing compound, or molecules of oxygen-absorbing compounds having one different type may be mixed.

The number average molecular weight of the isocyanate compound is preferably 100 to 10,000, more preferably 160 to 5,000. When the number average molecular weight is smaller than the above range, precipitation is likely to occur when mixed with a resin or resin composition. If the number average molecular weight is larger than the above range, when mixed with a resin or resin composition, the viscosity of the mixture increases, making it necessary to contain a large amount of diluting solvent, making it difficult to obtain a thick film or layer, Coating suitability tends to deteriorate.

(Hydroxy group-containing compound)
The hydroxyl group-containing compound is a compound from which the organic group 2 described above is derived, and has two or more hydroxyl groups.
Examples of the hydroxyl group-containing compound include polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, phenoxy resins, and urethane chain-extended polyols thereof. Among these, polyether polyols and polyolefin polyols are preferred.
In order to prevent odor generation, the hydroxyl group-containing compound preferably has no double bond in the aliphatic chain of the main skeleton or has two hydroxyl groups. It is preferable to have a hydroxyl group at the end because many of them are easily available, but it is not necessary to have it at the end.
In the present invention, one or more selected from the group consisting of these can be used as the hydroxyl group-containing compound from which the organic group 2 described above is derived. When two or more types are used, two types may be used in the same molecule of the oxygen-absorbing compound, or molecules of oxygen-absorbing compounds having one different type may be mixed.
The number average molecular weight of the hydroxyl group-containing compound is preferably 500 to 10,000, more preferably 750 to 5,000, even more preferably 1,000 to 3,000. When the number average molecular weight is smaller than the above range, precipitation is likely to occur when mixed with a resin or resin composition. If the number average molecular weight is larger than the above range, when mixed with a resin or resin composition, the viscosity of the mixture increases, making it necessary to contain a large amount of diluting solvent, making it difficult to obtain a thick film or layer, Coating suitability tends to deteriorate.

- Polyhydric alcohols Polyhydric alcohols are monomers having two or more hydroxyl groups.
Specific examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, cyclohexanedimethanol, 1, 8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3- Examples include diols such as pentanediol, 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, and 2,2'-oxydiethanol, glycerin, mannitol, and sorbitol.
Among the above, ethylene glycol is preferred from the viewpoint of oxygen absorption.

-Polyolefin polyol Polyolefin polyol is a polyolefin resin having two or more hydroxyl groups.
Specific examples of polyolefin polyols include those whose main skeleton is polyethylene, polypropylene, polybutylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth)acrylate copolymer. Examples include polyolefins having a hydroxyl group, such as a polymer, an ethylene-(meth)acrylic acid copolymer, and an ethylene-propylene copolymer.
Among these, those having a main skeleton of ethylene-vinyl acetate copolymer or hydrogenated polyisoprene are particularly preferred.

-Polyether polyol Polyether polyol is a polyether resin having two or more hydroxyl groups.
Polyether polyols are obtained, for example, by dehydration condensation of the above-mentioned polyhydric alcohols and polyolefin polyols, and have a polyether structure in the main skeleton and a hydroxyl group.
Specific examples of polyether polyols include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene ether diol, polypropylene ether diol, polybutylene ether diol, glycerin-modified polyether polyols, and the like. Among these, polypropylene ether diol is particularly preferred.

- Polyester polyol Polyester polyol is a polyester resin having two or more hydroxyl groups.
Polyester polyols are obtained, for example, by the esterification reaction of various polyhydric carboxylic acids or their derivatives with the above-mentioned polyhydric alcohols, polyolefin polyols, polyether polyols, etc., and have a polyester structure in the main skeleton and hydroxyl groups. has.
Specific examples of polyhydric carboxylic acids include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, and glutaric acid. acid, 1,4-cyclohexanedicarboxylic acid, trimellitic acid, etc., and derivatives of these polyhydric carboxylic acids include esterified products, acid anhydrides, acylated products, etc.
Among the above, polyester polyols containing two or more types of polyhydric alcohols and two or more types of polyhydric carboxylic acids in combination are preferred in order to reduce crystallinity.

- Polycarbonate polyol Polycarbonate polyol is a polycarbonate resin having two or more hydroxyl groups.
Polycarbonate has a polyol-derived portion in its main skeleton, but this polyol-derived portion may be derived from the above-mentioned polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, and the like.
Among these, polycarbonate polyols containing two or more types of polyhydric alcohols are preferred in order to reduce crystallinity.

- Poly(meth)acrylic ester polyol Poly(meth)acrylic ester polyol is a (meth)acrylic ester (co)polymer having two or more hydroxyl groups.
Poly(meth)acrylic acid ester polyols include, for example, 2-hydroxyethyl methacrylate, and (meth)acrylic esters having a hydroxyl group synthesized from one (meth)acrylic acid or its derivative and one diol. It can be obtained by polymerizing the hydroxyl group-containing monomers with each other or by copolymerizing them with a (meth)acrylic acid ester having no hydroxyl group.
The diols mentioned above, polyolefin polyols, polyether polyols, etc. can be used as diols for synthesizing (meth)acrylic esters having hydroxyl groups.
Among these, poly(meth)acrylic acid ester copolymers using 2-hydroxyethyl methacrylate are preferred.

・Phenoxy resin Phenoxy resin is a resin obtained by reacting a polyhydric phenol compound and a polyhydric epoxy compound, and has a structure in which an aliphatic hydroxyl group is formed at the bond where an aromatic hydroxyl group and an epoxy group have reacted. are doing.
As phenoxy resins, those obtained by reacting bisphenols with diglycidyl etherified bisphenols are easily available and common.
Examples of polyhydric phenol compounds include bisphenol A and bisphenol F, and examples of polyhydric epoxy compounds include bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.
Among these, phenoxy resin using bisphenol A is preferred.
The terminal of the phenoxy resin may be an aromatic hydroxyl group or an epoxy group.

- Urethane chain extended polyol Urethane chain extended polyol is a polyol having two or more hydroxyl groups obtained by elongating the above-mentioned hydroxyl group-containing compound with a urethane chain.
The urethane chain-elongated polyol can be obtained, for example, by subjecting the various hydroxyl group-containing compounds mentioned above to a polymerization reaction with the above-mentioned isocyanate-based compound to elongate the urethane chain. Further, if necessary, diamines or amino alcohols may be used in combination for polymerization.
Among the above, preferred are urethane chain-elongated polyols obtained by reacting the various hydroxyl group-containing compounds described above having hydroxyl groups at both ends with a diisocyanate compound.

(Specific examples of oxygen-absorbing compounds)
Specific oxygen-absorbing compounds are illustrated below.
3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-indenol represented by formula (1) and 3a,4,5,6, represented by formula (1-b) 7,7a-hexahydro-4,7-methano-1H-indenamine and 3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-indene represented by formula (1-c) -1-ol is an example of an oxygen-absorbing compound having one unsaturated five-membered ring, one organic group 1, and one organic group 1 having a hydroxyl group or an amino group as a functional group having active hydrogen. It is.

（式中、ａは１以上の数であり、Ｒ¹は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含み、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） The oxygen-absorbing compound represented by formula (2) has, for example, a hydroxyl group, which is a functional group having an active hydrogen, on organic group 1 of the oxygen-absorbing compound represented by formula (1), and the origin of organic group 2. The isocyanate group of R ¹ (NCO) _a , which is an isocyanate compound, reacts, the active hydrogen of the hydroxyl group is substituted, and the a number of unsaturated five-membered rings and the organic group 1 are bonded via R ¹ . It is an oxygen-absorbing compound that can be obtained by

(In the formula, a is a number of 1 or more, R ¹ is an organic group having 1 or more carbon atoms, contains at least an alkylene and/or phenylene structure, and further includes polyhydric alcohols, polyolefin polyols, polyether polyols) , polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, phenoxy resins, and urethane chain-extended polyols thereof.)

（式中、ｆは０以上の数であり、Ｒ⁴とＲ⁵の各々は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含む有機基であり、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） In the oxygen-absorbing compound represented by formula (5), a=2 in formula (2), and R ¹ is, for example, an isocyanate compound OCN-R ⁴ -NCO, a hydroxyl group-containing compound HO-R ⁵ It is an oxygen-absorbing compound derived from -OH and containing a structure formed by the reaction of the two.

(In the formula, f is a number of 0 or more, each of R ⁴ and R ⁵ is an organic group having 1 or more carbon atoms, an organic group containing at least an alkylene and/or phenylene structure, and a polyvalent Derived from one or more selected from the group consisting of alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, phenoxy resins, and these urethane chain-extended polyols structure.)

（式中、ｂとｃの各々は１以上の数であり、Ｒ²は、炭素数１以上の有機基であり、少な
くともアルキレンおよび／またはフェニレン構造を含み、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） The oxygen-absorbing compound represented by formula (3) includes, in formula (2), for example, R ¹ is derived from an isocyanate-based compound and a hydroxyl group-containing compound, and contains a structural moiety produced by the reaction of the two, and It is an oxygen-absorbing compound in which the excess hydroxyl group contains a hydroxyl group due to residual or chemical modification.

(In the formula, each of b and c is a number of 1 or more, R ² is an organic group having 1 or more carbon atoms, contains at least an alkylene and/or phenylene structure, and further includes polyhydric alcohols, polyolefin polyols, etc.) , polyether polyol, polyester polyol, polycarbonate polyol, poly(meth)acrylate polyol, phenoxy resin, and a structure derived from one or more types selected from the group consisting of these urethane chain-extended polyols. can.)

（式中、ｄとｅの各々は１以上の数であり、Ｒ³は、炭素数１以上の有機基であり、少なくともアルキレンおよび／またはフェニレン構造を含み、さらに、多価アルコール類、ポリオレフィンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ（メタ）アクリル酸エステルポリオール、フェノキシ樹脂、およびこれらのウレタン鎖伸長ポリオールからなる群から選ばれる１種または２種以上に由来する構造を含むことができる。） The oxygen-absorbing compound represented by formula (4) includes, in formula (2), for example, R ¹ is derived from an isocyanate-based compound and a hydroxyl group-containing compound, and contains a structural moiety produced by the reaction of the two, and Oxygen-absorbing compounds in which the excess isocyanate groups contain residual or chemically modified isocyanate groups.

(In the formula, each of d and e is a number of 1 or more, R ³ is an organic group having 1 or more carbon atoms, contains at least an alkylene and/or phenylene structure, and further includes polyhydric alcohols, polyolefin polyols, etc. , polyether polyol, polyester polyol, polycarbonate polyol, poly(meth)acrylic acid ester polyol, phenoxy resin, and a structure derived from one or more types selected from the group consisting of these urethane chain-extended polyols. can.)

[Oxidation promoting catalyst]
The oxidation-promoting catalyst is a compound that promotes the action of an oxygen-absorbing compound absorbing oxygen molecules and being oxidized.
Examples of the oxidation-promoting catalyst include peroxides and compounds containing cations made of transition metals.
Specific examples of the peroxide include hydrogen peroxide and the like.
The compound containing a cation consisting of a transition metal is preferably a metal soap consisting of a transition metal-containing compound capable of releasing a cation or complex of a transition metal atom, and an anion or a ligand consisting of a fatty acid.
As the transition metal, cobalt, manganese, iron, nickel, copper, etc. are preferable, and as the anion or ligand, an anion or a ligand consisting of stearic acid, naphthenic acid, octylic acid, acetylacetonate, etc. is preferable.
The oxidation promoting catalyst includes a cation consisting of one or more transition metals selected from the group consisting of the above transition metals, and one or more types selected from the group consisting of the long chain fatty acids above. A metal soap formed in combination with an anion consisting of a fatty acid can be used. Specific compounds include cobalt octylate, cobalt acetylacetone (II), cobalt acetylacetone (III), manganese acetylacetone (III), iron acetylacetone (III), and the like.

[Modifier]
The modifier is a compound having a functional group that reacts with the oxygen-absorbing compound when the oxygen-absorbing compound has a functional group, and various reactive monomers and resins can be used.
By including the modifier in the oxygen-absorbing adhesive composition, the oxygen-absorbing compound can be bonded to other components in the oxygen-absorbing adhesive composition, and the oxygen-absorbing property in the oxygen-absorbing adhesive composition can be improved. The content of the compound and the hardness of the cured product of the oxygen-absorbing adhesive composition can be adjusted.

For example, when the oxygen-absorbing compound has a hydroxyl group or an isocyanate group, a modifier consisting of an isocyanate-based compound and/or a hydroxyl group-containing compound can be used.
When the oxygen-absorbing adhesive composition is urethane-based, the equivalent ratio NCO/OH of the oxygen-absorbing adhesive composition is preferably 0.5 or more and 8 or less. If it is smaller than the above range, the oxygen-absorbing adhesive composition may not be sufficiently cured and sufficient lamination strength (adhesive strength) may not be obtained; if it is larger than the above range, the oxygen-absorbing adhesive composition There is a risk that the pot life of the agent composition will become too short.

(Isocyanate compound for modifier)
As the isocyanate compound for the modifier, the isocyanate compound used in the synthesis of the oxygen-absorbing compound can be used, and any of aromatic isocyanates, aliphatic isocyanates, and urethane chain elongated isocyanates can be used. . Furthermore, in order to cure the oxygen-absorbing adhesive composition, it is preferable that the adhesive composition has two or more isocyanate groups in one molecule. However, an isocyanate compound having one isocyanate group in one molecule can also be used in combination within a range that does not impede the sufficient effect of the oxygen-absorbing adhesive composition.
As the isocyanate compound having two or more isocyanate groups in one molecule, biuret hexamethylene diisocyanate is particularly preferred.

Specific isocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, xylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, phenylene diisocyanate, diphenyl ether diisocyanate, and polymethylene diisocyanate. phenyl Examples include polyisocyanates, trimethylolpropane adducts, biuret bodies, allophanate bodies, isocyanurate bodies (trimers), and various derivatives thereof. Among these, biurette forms of toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate are preferred.

(Hydroxy group-containing compound for modifier)
As the hydroxyl group-containing compound for the modifier, the hydroxyl group-containing compound used in the synthesis of the oxygen-absorbing compound can be used, and any of aromatic hydroxyl group-containing compounds, aliphatic hydroxyl group-containing compounds, and these urethane chain-elongated polyols can be used. Can be used. Further, in order to cure the oxygen-absorbing adhesive composition, it is preferable that the adhesive composition has two or more hydroxyl groups in one molecule. However, a hydroxyl group-containing compound having one hydroxyl group per molecule can also be used in combination within a range that does not impede the sufficient effect of the oxygen-absorbing adhesive composition.
As the hydroxyl group-containing compound having two or more hydroxyl groups in one molecule, any of aromatic hydroxyl group-containing compounds and aliphatic hydroxyl group-containing compounds can be used, and may be alcohol-based or phenol-based.
As the isocyanate compound having two or more isocyanate groups in one molecule, particularly preferred are polyalkylene ether diols and urethane chain-extended polyols such as polyalkylene ether diols.

[Dilution solvent]
The diluting solvent is not particularly limited as long as it can uniformly dissolve or disperse the oxygen-absorbing compound and the oxidation-promoting catalyst, make the oxygen-absorbing adhesive composition uniform, and is compatible with the dry lamination process. A solvent, a ketone diluent, a hydrocarbon diluent, etc. can be used.
Specific examples of ester-based diluting solvents include ethyl acetate, butyl acetate, etc., specific examples of ketone-based diluting solvents include methyl ethyl ketone, and specific examples of hydrocarbon-based diluting solvents include toluene, etc. . Among these, ethyl acetate is easy to use and is preferred.

[Various additives]
The oxygen-absorbing adhesive composition can contain various additives as necessary.
For example, curing accelerators, curing modifiers to extend pot life, and to suppress the decline in oxygen absorption during storage and use of oxygen-absorbing adhesive compositions and before the contents are placed in packages. Antioxidants, adhesion aids, tackifiers, leveling agents, ultraviolet absorbers, and antifoaming agents can also be added.

(hardening accelerator)
As the curing accelerator, any one can be used without particular limitation as long as it accelerates the curing reaction of the oxygen-absorbing adhesive composition.
Specific curing accelerators include metal-containing compounds such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dibutyltin dimaleate, tetrabutyl titanate, and tetraisopropyl titanate, and 1,8-diaza-bicyclo(5,4 , 0) undecene-7, 1,5-diazabicyclo(4,3,0)nonene-5, tertiary amines such as triethanolamine, etc., and one or more types selected from the group consisting of these. can be used.

(Curing regulator)
When the pot life of the oxygen-absorbing adhesive composition is shortened by the oxidation-promoting catalyst it contains, the pot life can be extended by using a curing modifier in combination.
As a specific curing regulator, phosphoric acids are preferable, and examples thereof include orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, and ester derivatives thereof, and one or more types selected from the group consisting of these are used. be able to.
The amount of the reaction regulator added is preferably 200 ppm or more and 400 ppm or less based on the resin component of the oxygen-absorbing adhesive composition. When the amount is less than the above range, it is difficult to obtain the effect of lengthening the pot life, and when it is more than the above range, there is a possibility that curing of the oxygen-absorbing adhesive composition may be inhibited.

(Antioxidant)
This method suppresses the deterioration of oxygen absorption during storage and use of the oxygen-absorbing adhesive composition, and furthermore, in the process before the package made using the oxygen-absorbing adhesive composition accommodates the contents. The oxygen-absorbing adhesive composition may contain an antioxidant in order to maintain high oxygen-absorbing properties after containing the contents.
Specific antioxidants include phenolic, lactone, thioether, gallic acid, ascorbic acid, erythorbic acid, catechin, dibutylhydroxytoluene, tocopherol, citric acid, butylhydroxyanisole, phosphite, hindered amine, Examples include aromatic amines, and one or more selected from the group consisting of these can be used.
In addition, if it is assumed that heat or light is used as a trigger for the development of oxygen absorption, it is preferable to use antioxidants with low heat resistance and light resistance such as ascorbic acid and tocopherol, and antioxidants with high heat resistance such as phenols. , it is not preferable to use an antioxidant with high light resistance.
The amount of the antioxidant added is preferably 10 ppm or more and 10,000 ppm or less relative to the oxygen-absorbing compound. When the amount is less than the above range, the antioxidant effect tends to be insufficient, and when it is more than the above range, there is a risk that the oxygen absorbency may be reduced.

(adhesion aid)
A silane coupling agent is preferable as an adhesion aid for assisting adhesive strength.
Examples of the silane coupling agent include γ-glycidoxypropyltrialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-glycidoxypropylmethyldialkoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane. Silane, γ-aminopropyltrialkoxysilane, γ-aminopropylmethyldialkoxysilane, N-(β-aminoethyl)-γ-aminopropyltrialkoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyl Examples include dialkoxysilane, N-butyl-3-amino-2-methylpropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, and γ-mercaptopropylmethyldialkoxysilane, and the alkoxy group is a methoxy group or an ethoxy group. Preferably, one or more types selected from the group consisting of these can be used.

(Tackifier)
Examples of the tackifier include paraffin wax, polyethylene wax, rosin, rosin glycerin ester, terpene, and alkylphenol, and one or more types selected from the group consisting of these can be used.

(Leveling agent)
Examples of the leveling agent include acrylic polymer type, modified silicone type, and acetylene diol type, and one or more types selected from the group consisting of these can be used.

(Ultraviolet absorber)
Examples of the ultraviolet absorber include benzotriazole type, hydroxyphenyltriazine type, and hindered amine type, and one or more types selected from the group consisting of these can be used.

(antifoaming agent)
Examples of antifoaming agents include surfactants and polyether-modified silicone oils, and one or more types selected from the group consisting of these can be used.

《Method for preparing oxygen-absorbing adhesive composition》
The oxygen-absorbing adhesive composition can be produced by mixing all the constituent components such as an oxygen-absorbing compound, an oxidation-promoting catalyst, and if necessary, a modifier, a diluting solvent, and various additives. Alternatively, it can be manufactured by mixing an oxygen-absorbing compound, an oxidation-promoting catalyst, and, if necessary, a modifier, a diluting solvent, various additives, etc., into an existing adhesive composition.
The above-mentioned mixing method and the order in which the components are mixed are not particularly limited, and the methods and mixing order used in preparing general adhesive compositions can be applied.
Specific mixing methods include a method of dissolving and mixing in a solvent and a method of melting and kneading. At this time, it is preferable to adjust the heating temperature in order to improve solubility and dispersibility.

《How to use the oxygen-absorbing adhesive composition》
There is no particular limitation on the method of using the oxygen-absorbing adhesive composition, and a general method of using it as an adhesive can be applied.
Examples include a non-solvent lamination method in which the coating is heated to obtain an appropriate viscosity, and a dry lamination method in which the coating viscosity is adjusted to an appropriate coating viscosity by adding a diluting solvent or other compounded adhesive.
When forming an oxygen-absorbing adhesive layer using an oxygen-absorbing adhesive composition, the coating amount is preferably 2 to 5 g/m ² , more preferably 3 to 5 g/m ² . If it is less than the above range, there is a risk that sufficient oxygen absorbency may not be obtained, and if it is more than the above range, the oxygen absorption property will not change much, leading to cost disadvantages, which is not preferable.

The oxygen-absorbing laminate obtained by forming and adhering an oxygen-absorbing adhesive layer using an oxygen-absorbing adhesive composition is usually kept at a temperature of 20°C or higher and 50°C or lower for 2 days or more and 5 days. It is preferable to perform the following aging.
In addition, when aging is performed, it is preferable to perform the aging at the lowest possible temperature or under an inert gas atmosphere in order not to reduce the oxygen absorbing property of the oxygen-absorbing laminate.
When storing the produced oxygen-absorbing laminate, it is preferably stored at a temperature of 10° C. or lower or under an inert gas atmosphere so as not to reduce the oxygen-absorbing property of the oxygen-absorbing laminate.

《About objects that can be bonded》
There are no particular limitations on the objects that the oxygen-absorbing adhesive composition can adhere to, such as resin molded products, resin films, paper, metals, metal foils, inorganic vapor-deposited film surfaces, and inorganic oxide vapor-deposited film surfaces. Adhesion is possible.

Specific examples of the resin for the resin film include polyester resins such as polyethylene terephthalate (PET), polyamide resins such as various nylons, polyethylene resins, polypropylene resins, cyclic polyolefin resins, polystyrene resins, and acrylonitrile-styrene resins. Polymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyolefin resin such as polybutene resin, polyvinyl chloride resin, polycarbonate resin, polyimide resin, polyamideimide resin, diallyl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, cellulose resin, poly(meth)acrylic resin, polyvinylidene chloride resin, acetal resin, fluorine resin Examples include resin.

Specific examples of paper include, for example, bleached or unbleached paper base materials with strong size properties, paper base materials for paper layers, or paper base materials such as pure white roll paper, kraft paper, paperboard, coated paper, processed paper, and milk base paper. , and others.
Specific examples of metal foil include aluminum foil, copper foil, stainless steel foil, and the like.
A specific example of the metal of the inorganic deposited layer is aluminum.
Specific examples of inorganic oxides for the inorganic vapor deposition layer include silica, alumina, indium tin oxide, zinc oxide, tin oxide, titanium oxide, zirconium oxide, vanadium oxide, barium oxide, chromium oxide, silicon nitride, silicon carbide, etc. Can be mentioned. Among these, silica and alumina are preferred.

≪Sealant layer≫
Since the sealant layer is heat-sealed when producing the package, it is preferable that the sealant layer contains a heat-sealable resin.
The sealant layer may be composed of a single layer, or may have a multilayer composition of two or more layers having the same or different compositions.
The thickness of the sealant layer is preferably 10 μm to 200 μm, more preferably 30 μm to 100 μm.

Further, the sealant layer may contain any additives as long as the effects of the present invention are not significantly impaired. Additives include various resin additives that are commonly used to adjust the moldability, productivity, and various physical properties of resin films, such as anti-blocking agents, slip agents, pigments, flow control materials, and flame retardants. , fillers, ultraviolet absorbers, surfactants, etc.

[Heat-sealable resin]
Generally, heat-sealable resins are made using polyolefin resins or polyolefin resins containing unsaturated carboxylic acids or their anhydrides such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Resins such as acid-modified polyolefin resins, polyvinyl acetate resins, poly(meth)acrylic resins, polyvinyl chloride resins, and others that are acid-modified by graft polymerization or copolymerization can be used. These resins can be used alone or in combination.
In the case of packaging materials for packaging containers that can withstand high temperatures, heat-resistant heat-sealable resins of high grade with high softening point, heat resistance, and oxidation resistance are used to withstand high-temperature processing. Also, the oxidative deterioration resistance may be improved.
In the present invention, polyolefin resins such as polyethylene resins and polypropylene resins are preferable among the above heat-sealable resins. When a balance between heat sealability, heat resistance, and oxidative deterioration resistance is required, among the above, highly heat-resistant polyolefin resins with a softening point of 120°C or higher and 170°C or lower are preferred; Among these, highly heat resistant polyethylene resins and highly heat resistant polypropylene resins are more preferred.

(Polyolefin resin)
Specific examples of polyolefin resins that are heat-sealable resins include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and polyolefin resins polymerized using metallocene catalysts. Ethylene-α-olefin copolymer, polypropylene resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene -Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene (co)polymer, butene (co)polymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid Examples include copolymers, cyclic olefin (co)polymers such as polynorbornene, and the like. The copolymer may be a random or block copolymer.

Polyolefin resins are classified into, for example, polyethylene resins and polypropylene resins, depending on the skeleton of the monomer used to synthesize the polyolefin, and may be copolymers. In the present invention, "resin" is added as a generic term for various types of polyethylene, and for example, polyethylene resin is also written as a generic term for various polyethylenes.
Polyolefins produced by polymerizing α-olefins such as ethylene, propene, 1-butene, 1,3-butadiene, and 1-hexene are polyethylene resins, polypropylene resins, and polybutylene resins, respectively. It is called resin, polybutadiene resin, polyhexene resin, etc.
Polymerization methods include, for example, high-pressure polymerization for low-density polyethylene, and low-pressure polymerization for linear low-density polyethylene (gas-phase polymerization using a Ziegler-Natta catalyst or liquid-phase polymerization using a metallocene catalyst). Polymerization methods such as the slurry method, the solution method, and the gas phase polymerization method are common.

《Method for forming sealant layer》
The method for forming the sealant layer is not particularly limited, and conventionally known methods for stacking sealant layers can be applied.
A sealant film consisting of one layer or two or more layers for the sealant layer may be prepared in advance, and the sealant film may be laminated by adhering to other layers constituting the laminate via an adhesive or the like. As a method for producing a sealant film, one or more resin compositions may be melt-extruded and formed into a film by an inflation method, or melt-extruded onto a roll by an extrusion method using T-die molding or the like. It may be constricted to form a film.
Here, it is preferable that one side of the produced sealant film is subjected to corona treatment, and then the corona treated side faces the side to be laminated and is bonded and laminated.
Alternatively, the resin composition for forming the sealant layer is melted, melted (co)extruded, and poured onto the layer to be laminated, and T-die molding using a feed block method or multi-manifold method is used. A single or multilayer sealant layer may be laminated on other layers constituting the laminate by an extrusion method.
In either method, a multilayer sealant film can be produced by co-melt extrusion using resin compositions having the same or different compositions.

≪General-purpose adhesive layer≫
A general-purpose adhesive layer or an anchor coat layer can be included between the layers constituting the oxygen-absorbing laminate.
For example, the sealant layer can be formed by adhering a sealant film for the sealant layer via a general-purpose adhesive layer or an anchor coat layer.
The general-purpose adhesive layer may be a layer (extruded resin layer) formed by, for example, a (co)extrusion lamination method, a T-die (co)extrusion method, etc. in which an adhesive resin composition is melt-extruded, It may be a layer formed by dry lamination using a dry lamination adhesive (dry laminate layer).
Examples of the resin contained in the above-mentioned adhesive resin composition include polyolefin resins and polyolefin resins combined with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Acid-modified polyolefin resins, polyvinyl acetate resins, poly(meth)acrylic resins, polyvinyl chloride resins, and other resins are acid-modified by graft polymerization or copolymerization using acids or their anhydrides. can be used. These resins can be used alone or in combination.

Specific examples of polyolefin resins include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and ethylene-α-olefin polymerized using a metallocene catalyst. Polymer, polypropylene resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer , ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene (co)polymer, butene (co)polymer, polyisoprene, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer , cyclic olefin (co)polymers such as polynorbornene, and the like. The copolymer may be a random or block copolymer.
Polyolefin resins are classified into, for example, polyethylene resins and polypropylene resins, depending on the skeleton of the monomer used to synthesize the polyolefin, and may be copolymers. In the present invention, "resin" is added as a generic term for various types of polyethylene, and for example, polyethylene resin is also written as a generic term for various polyethylenes.
Polyolefins produced by polymerizing α-olefins such as ethylene, propene, 1-butene, 1,3-butadiene, and 1-hexene are polyethylene resins, polypropylene resins, and polybutylene resins, respectively. It is called resin, polybutadiene resin, polyhexene resin, etc.

The general-purpose adhesive layer may contain additives such as antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, anti-blocking agents, flame retardants, crosslinking agents, colorants, etc., to the extent that the characteristics of the present invention are not impaired. can contain agents.
The thickness of the general-purpose adhesive layer is not particularly limited, but is preferably 1 g/m ² or more and 20 g/m ² or less, or 1 μm or more and 20 μm or less. By setting the thickness of the extruded resin layer within the above numerical range, it is possible to have stable adhesive strength.
In addition, examples of dry laminating adhesives constituting a general-purpose adhesive layer formed by dry lamination include two-component curable urethane adhesives, polyester urethane adhesives, and polyether urethane adhesives. , acrylic adhesive, polyester adhesive, polyamide adhesive, polyvinyl acetate adhesive, epoxy adhesive, rubber adhesive, and others can be used.

The anchor coat layer is a layer formed by applying and drying an anchor coat agent, and can improve the adhesion between adjacent layers.
Examples of the anchor coating agent include anchor coating agents made of any resin having a heat resistance temperature of 135° C. or higher, such as vinyl-modified resin, epoxy resin, urethane resin, polyester resin, polyethyleneimine, and the like.
Among the above, in particular, a curable anchor coating agent containing a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups in one molecule as a main ingredient and an isocyanate compound as a curing agent. is preferred.
Further, a silane coupling agent may be used in combination, and nitrified cotton may be used in combination to improve heat resistance. The thickness of the anchor coat layer is not particularly limited, but is preferably, for example, 0.05 μm or more and 1 μm or less.

≪Functional layer≫
Examples of the functional layer include an auxiliary barrier layer, a fragrance layer, a light shielding layer, and a reinforcing layer.

[Auxiliary barrier layer]
The auxiliary barrier layer is a layer made of resin that increases oxygen gas and provides barrier properties against water vapor and the like.
Specifically, the above resins include, for example, polyacrylic resin, polymethacrylic resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, polycarbonate resin, polyethylene terephthalate resin, or its ethylene and/or a resin in which a part of the terephthalate component is copolymerized or modified with other di- or higher polyhydric alcohol components or dicarboxylic acid components, polyester resins such as polyethylene naphthalate resins, polyamide resins, ethylene- Resins such as saponified vinyl acetate copolymers, polyvinyl alcohol resins, polyvinyl chloride resins, polyvinylidene chloride resins, and others can be used.

Among the above resins, it is preferable to use resins that have aroma retention properties and barrier properties against oxygen gas or water vapor, etc. Specifically, examples include saponified ethylene-vinyl acetate copolymers, polyamide It is preferable to use resin, polyacrylonitrile-based resin, polyester-based resin, etc., which is rich in aroma retention properties, barrier properties, etc.

[Fragrance-preserving layer]
The aroma-retaining layer is a layer that has low adsorption of flavor components contained in the contents to be filled and packaged, is rich in aroma-retaining properties, and also has the property of not causing off-taste, off-odor, etc.

[Light blocking layer]
The light-shielding layer is made of a light-shielding material and is a layer that prevents ultraviolet rays and/or visible light from reaching the contents and deteriorating the contents due to the light.
The light-shielding layer is made of white ink whose main component is titanium oxide, etc., black ink whose main component is carbon black, etc., gray ink whose main component is aluminum paste, or colored resin with a colorant that blocks light by adding pigments, dyes, etc. It can be formed using a film, metal foil, metal vapor deposition film, or the like.
Note that, as described above, when a metal foil such as aluminum foil is used as the barrier layer, the barrier layer can also serve as a light-shielding layer.
These light-shielding materials can be used alone or in combination of two or more.
When white ink, black ink, or gray ink is used, the thickness of the light shielding layer is preferably 4 μm or more and 12 μm or less, more preferably 5 μm or more and 9 μm or less.
In the case of aluminum foil, it is preferably 5 μm to 30 μm, in the case of a metal vapor deposited film, it is preferably 50 Å to 3000 Å, more preferably 100 Å to 1000 Å, and in the case of a colorant-colored resin film, it is preferably 5 μm to 300 μm, and 10 μm to 100 μm is more preferable.

[Reinforcement layer]
The reinforcing layer is a layer that imparts mechanical strength, deformation resistance, drop impact resistance, pinhole resistance, heat resistance, sealability, quality integrity, workability, hygiene, etc. to the laminate. .
The reinforcing layer may be formed from any of extrusion-formed or inflation-formed resin films, resin coating films, synthetic paper, and the like.

Specifically, the resin contained in the reinforcing layer includes, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer. Coalescence, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin , vinyl chloride-vinylidene chloride copolymer, poly(meth)acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS) polyester resins, polyamide resins, polycarbonate resins, polyvinyl alcohol resins, saponified ethylene-vinyl acetate copolymers, fluorine resins, diene resins, polyacetal resins, polyurethane resins, cellulose, Known resins such as nitrocellulose and others can be used.
Moreover, the above-mentioned resin film can be used either unstretched or uniaxially or biaxially stretched.
The thickness of the reinforcing layer is not particularly limited, but can be selected from a range of several μm to 300 μm.

<About the method for producing the oxygen-absorbing laminate>
A method for manufacturing an oxygen-absorbing laminate using the above materials will be described. The manufacturing method shown below is one example and does not limit the present invention.
The layers constituting the oxygen-absorbing laminate are laminated using a lamination method used when manufacturing ordinary packaging materials, such as wet lamination, dry lamination, solvent-free dry lamination, extrusion lamination, or T. This can be carried out by any method such as a die co-extrusion method, a co-extrusion lamination method, an inflation method, or the like.
The oxygen-absorbing laminate of the present invention has chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. It is also possible to perform secondary processing for the purpose of imparting.
Examples of secondary processing include embossing, painting, adhesion, printing, metallization (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Further, the laminate of the present invention can also be subjected to lamination processing (dry lamination or extrusion lamination), bag making processing, and other post-processing processing.

When performing the above-described lamination, if necessary, the surface of each layer may be subjected to pretreatment such as corona treatment or ozone treatment. In addition, for example, anchor coating agents such as isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based, etc., or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, etc. Anchor coating agents such as laminating adhesives such as , etc. can be optionally used.

As long as the printing ink layer, printing ink component shielding resin layer, inorganic oxygen barrier layer, oxygen absorbing adhesive layer, and sealant layer are laminated in this order, the formation and lamination order of each layer is arbitrary. That's fine.

For example, an example will be described in which an oxygen-absorbing laminate having a layer configuration of printing ink layer/printing ink component shielding resin layer/inorganic oxygen barrier layer/oxygen-absorbing adhesive layer/sealant layer is produced.
For example, first, a printing ink layer is provided on the resin surface of a resin film with an inorganic vapor deposited layer on one side, which is a film having a printing ink component shielding resin layer and an inorganic oxygen barrier layer, by a printing method such as a gravure printing method or a flexographic printing method.
Then, an oxygen-absorbing adhesive composition is applied to the surface of the inorganic vapor-deposited layer and dried to form an oxygen-absorbing adhesive layer, and a sealant film for a sealant layer is adhered and laminated.
Further, aging processing is performed as necessary.

Alternatively, first, an oxygen-absorbing adhesive composition is coated on the inorganic vapor-deposited layer surface of a resin film with an inorganic vapor-deposited layer on one side, which is a film having a printing ink component shielding resin layer and an inorganic oxygen barrier layer, and dried. An adhesive layer is formed, and a sealant film for the sealant layer is adhered and laminated.
Further, aging processing is performed as necessary.
Then, a printing ink layer is formed on the printing ink component shielding resin layer by a printing method such as a gravure printing method or a flexographic printing method.
In this way, an oxygen-absorbing laminate can be obtained.
Then, a printing ink layer is formed on the printing ink component shielding resin layer by a printing method such as a gravure printing method or a flexographic printing method.
In this way, an oxygen-absorbing laminate can be obtained.

<<Oxygen-absorbing packaging material>>
The oxygen-absorbing packaging material is a packaging material made from the oxygen-absorbing laminate of the present invention.
The oxygen-absorbing packaging material may have the same layer structure as the oxygen-absorbing laminate, and may further include layers having various functions, if necessary.

The present invention will be explained in more detail below by giving Examples and Comparative Examples.

The present invention will be explained in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited only to these Examples.

<Raw materials>
The main raw materials used in the examples are as follows.
[Raw material for oxygen-absorbing compounds]
- Polypropylene ether diol 1: manufactured by Sanyo Chemical Co., Ltd., SANNIX PP-1000. Number average molecular weight 1000.
- Polypropylene ether diol 2: SANNIX PK-400 manufactured by Sanyo Chemical Co., Ltd. Number average molecular weight 400.
- Hydroxyl group-terminated polyisoprene 1: manufactured by Idemitsu Kosan Co., Ltd., Poly ip. Number average molecular weight 2500.
- Hydroxyl group-terminated polybutadiene 1: Poly bd R15HT manufactured by Idemitsu Kosan Co., Ltd. Number average molecular weight 1200. Hydroxyl group-terminated 1,2 addition polymer of 1,3-butadiene.
- Toluene diisocyanate 1: Coronate T-65, manufactured by Tosoh Corporation.
- Oxygen-absorbing compound 1: 3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-inden-6-ol.
- Oxidation promoting catalyst solution 1: Octope AE, manufactured by Hope Pharmaceutical Co., Ltd. A 4% ethyl acetate solution of cobalt octylate, which is an oxidation promoting catalyst.
- Oxidation promoting catalyst solution 2: Acetope Mn (III) manufactured by Hope Pharmaceutical Co., Ltd. A 10% ethyl acetate solution of manganese(III) acetylacetone, which is a pro-oxidation catalyst.

[Printing ink]
・Printing ink 1: Rio Alpha R631 white manufactured by Toyo Ink Co., Ltd.

[General purpose adhesive]
- DL adhesive 1: Manufactured by Rock Paint Co., Ltd., two-component curing polyester polyurethane general-purpose adhesive for dry lamination, Ru-004/H-1.

[Printing ink component shielding resin layer/film for inorganic oxygen barrier layer]
- Transparent vapor-deposited PET film 1: IB-PET manufactured by Dai Nippon Printing Co., Ltd. Single-sided transparent alumina vapor deposited PET film. 12μm thick. The alumina vapor deposited layer above functions as an inorganic oxygen barrier layer.
・Transparent vapor-deposited nylon film 1: IB-ON manufactured by Dai Nippon Printing Co., Ltd. Single-sided transparent silica-deposited ON film. 15μm thick. The silica vapor deposited layer above functions as an inorganic oxygen barrier layer.

[Film for sealant layer]
- LLDPE film 1: Manufactured by Aicello Co., Ltd., unstretched linear low-density polyethylene film, N-165. 40 μm thick.

<Preparation of raw material solution>
(Synthesis of polyol 1 and preparation of polyol solution 1)
The following raw materials were added to a flask equipped with a nitrogen inlet tube, a stirrer, a rectification column, and a condenser, and dehydration condensation was carried out at an internal temperature of 180 to 200°C while stirring.
Ethylene glycol 53.8 parts by mass Neopentyl glycol 180.3 parts by mass 1,6-hexanediol 204.6 parts by mass Isophthalic acid 287.8 parts by mass Adipic acid 273.5 parts by mass The acid value of the reaction liquid solid content is 15 mgKOH/ When the temperature reached 200 g, the dehydration reaction was further progressed at 200 to 240° C. while blowing nitrogen.
When the acid value of the solid content of the reaction liquid became 10 mgKOH/g or less, the internal pressure was reduced to 30 Torr and the reaction was continued to proceed.
When the acid value of the solid content of the reaction liquid became 3 mgKOH/g or less, the reaction was terminated and the mixture was cooled to room temperature to obtain polyol 1.
The number average molecular weight of Polyol 1, which is the obtained polyester polyol, was 2,000.
Next, polyol 1 was dissolved in ethyl acetate to adjust the solid content to 60% by mass to obtain polyol solution 1.

(Synthesis of polyol 2 and preparation of polyol solution 2)
The following raw materials were charged into a flask equipped with a nitrogen inlet tube, a stirrer, and a condenser, heated while stirring, and refluxed for 6 hours.
Polypropylene ether diol 1 300.0 parts by mass Polypropylene ether diol 2 250.0 parts by mass Toluene diisocyanate 1 104.0 parts by mass Ethyl acetate 163.5 parts by mass The absorption of isocyanate groups must completely disappear in the infrared absorption spectrum. After confirming this, the synthesis was completed and cooled to obtain polyol 2.
The number average molecular weight of Polyol 2, which is the obtained urethane chain extended polyol, was 2,000.
Next, Polyol 2 was dissolved in ethyl acetate to adjust the solid content to 60% by mass to obtain Polyol Solution 2.

(Preparation of polyisocyanate solution 1)
The following raw materials were added to a flask equipped with a nitrogen inlet tube, a stirrer, and a condenser and stirred to obtain a polyisocyanate solution 1 with a solid content of 60% by mass.
Biuret form of hexamethylene diisocyanate 100.0 parts by mass Ethyl acetate 66.7 parts by mass

<Synthesis of oxygen-absorbing compound and preparation of oxygen-absorbing compound solution>
[Oxygen-absorbing compound 2]
First, the following raw materials were added to a flask equipped with a nitrogen inlet tube, a stirrer, and a condenser, and a reaction was carried out at an internal temperature of 80 to 90°C for 8 hours while stirring.
Oxygen-absorbing compound 1 100.0 parts by mass Isophorone diisocyanate 74.0 parts by mass After confirming that the absorption of the isocyanate group has completely disappeared by infrared absorption spectrum, the synthesis is completed, and the oxygen-absorbing compound is cooled. Compound 2 was obtained.
Then, oxygen absorbing compound solution 2 having a solid content of 80% by mass was prepared by dissolving oxygen absorbing compound 2 in ethyl acetate.

[Oxygen-absorbing compound 3]
First, the following raw materials were added to a flask equipped with a nitrogen inlet tube, a stirrer, and a condenser, and a reaction was carried out at an internal temperature of 80 to 90°C for 8 hours while stirring.
Oxygen-absorbing compound 1 100.0 parts by mass Polyisocyanate solution 1 212.5 parts by mass Synthesis was carried out after confirming that the content of NCO groups in the solid content of the reaction solution was approximately 0.64 mass% by the amine equivalent method. was completed, cooled, and the solvent was removed to obtain oxygen-absorbing compound 3.
Then, oxygen absorbing compound 3 was dissolved in ethyl acetate to prepare oxygen absorbing compound solution 3 having a solid content of 60% by mass.

[Oxygen-absorbing compound 4]
First, the following raw materials were added to a flask equipped with a nitrogen inlet tube, a stirrer, and a condenser, and a reaction was carried out at an internal temperature of 80 to 90°C for 8 hours while stirring.
Oxygen-absorbing compound 1 100.0 parts by mass Polyol solution 1 682.3 parts by mass Polyisocyanate solution 1 265.6 parts by mass Confirm that the absorption of isocyanate groups has completely disappeared by infrared absorption spectrum, and then proceed with the synthesis. Upon completion, cooling and removal of solvent, oxygen absorbing compound 4 was obtained.
Then, the oxygen-absorbing compound 4 was dissolved in ethyl acetate to prepare an oxygen-absorbing compound solution 4 having a solid content of 60% by mass.

[Oxygen-absorbing compound 5]
Oxygen-absorbing compound 5 was obtained in the same manner as for oxygen-absorbing compound 4, except that polyol solution 2 was used instead of polyol solution 1.
Then, the oxygen-absorbing compound 5 was dissolved in ethyl acetate to prepare an oxygen-absorbing compound solution 5 having a solid content of 60% by mass.

[Oxygen-absorbing compound 6]
The following raw materials were charged into a flask equipped with a nitrogen inlet tube, a stirrer, and a condenser, and the reaction was carried out at an internal temperature of 80 to 90°C for 6 hours while stirring.
Hydroxyl group-terminated polyisoprene 1 100.0 parts by mass Isophorone diisocyanate 4.7 parts by mass After confirming that the absorption of isocyanate groups has completely disappeared by infrared absorption spectrum, the synthesis is completed, and the urethane polyol is obtained by cooling. Oxygen-absorbing compound 6 was obtained.
The number average molecular weight of the obtained oxygen-absorbing compound 6 was 7,000.
Then, the oxygen-absorbing compound 6 was dissolved in ethyl acetate to prepare an oxygen-absorbing compound solution 6 having a solid content of 60% by mass.

Table 2 summarizes the charged composition of the reaction solution when oxygen-absorbing compounds 2 to 6 were synthesized.
Further, the charging compositions of oxygen-absorbing compound solutions 2 to 6 are summarized in Table 3.

<Preparation of oxygen-absorbing adhesive composition>
(Preparation of oxygen-absorbing adhesive composition A1)
The following raw materials were mixed and homogenized at room temperature to obtain oxygen-absorbing adhesive composition A1, and various evaluations were performed.
Oxygen-absorbing compound solution 2 100 parts by mass Polyol solution 1 100 parts by mass Polyisocyanate solution 1 10 parts by mass Oxidation promoting catalyst solution 1 1 part by mass Ethyl acetate 140 parts by mass

(Preparation of oxygen-absorbing adhesive compositions A2 to A9, B1 to B2)
According to the formulations in Table 4, oxygen-absorbing adhesive compositions A2 to A9 and B1 to B2 were obtained by operating in the same manner as oxygen-absorbing adhesive composition A1.

<Evaluation of oxygen-absorbing adhesive composition>
A test laminate film was produced using each of the oxygen-absorbing adhesive compositions obtained above, and a simple evaluation of the oxygen-absorbing adhesive compositions was performed.

[Preparation of test laminate film]
After applying the oxygen-absorbing adhesive composition to the PET film 1 using a bar coater so that the dry coating amount is 5.0 g/m ² and drying it, the LLDPE film 1 is laminated and heated on a hot plate at 60°C. A nip was performed on the top and aged at 25° C. for 2 days to obtain a laminate film for a test piece.

[Oxygen absorption]
A packaging bag was prepared by folding the test laminate film in half and heat-sealing the three sides so that the inner dimensions were 130 mm x 70 mm, and an oxygen sensor chip (non-destructive oxygen sensor chip manufactured by Precision Sensing) was placed in the packaging bag. and sealed the packaging bag.
Then, 26cc of air was injected into the packaging bag using a syringe, the injection part was repaired with adhesive tape, and the oxygen concentration was measured at the time of injection and after 14 days of storage in a constant temperature bath at 25°C, and the amount of oxygen absorbed was calculated. did.

[Lamination strength]
A strip-shaped test piece with a width of 15 mm was prepared from the test laminate film obtained above, and the laminate strength between the PET film 1 and the LLDPE film 1 was measured using a tensile tester at a tensile speed of 50 mm/min. was measured.

[Odor]
After the above oxygen absorption measurement, the packaging bag was opened and the odor was sensory evaluated according to the following evaluation criteria.
Evaluation criteria:
0: No odor 1: Faint odor 2: Weak odor 3: Moderate odor 4: Strong odor

<Preparation and evaluation of oxygen-absorbing laminate>
[Example 1]
Printing ink 1 was printed on the PET surface of transparent vapor-deposited PET film 1 by gravure printing so that the dry coating amount was 2 g/m ² to form a printing ink layer.
Next, the oxygen-absorbing adhesive A1 was applied to the other vapor-deposited surface of the transparent vapor-deposited PET film 1 so that the dry coating amount was 3 g/m ² and dried, and then the LLDPE film 1 was laminated by a dry lamination method. The laminate was aged at 40° C. for 3 days to obtain an oxygen-absorbing laminate having the following layer structure, and various evaluations were performed.
Layer structure: printing ink layer (2 g/m ² )/transparent vapor-deposited PET film 1 (12 μm thick) [PET film layer/transparent alumina vapor-deposited layer]/oxygen-absorbing adhesive composition A1 (3 g/m ² )/LLDPE film 1 (40μm thickness)

[Example 2]
An oxygen-absorbing laminate was obtained in the same manner as in Example 1 except that the transparent vapor-deposited PET film 1 was replaced with the transparent vapor-deposited nylon film 1, and evaluated in the same manner.
Layer structure: printing ink layer (2 g/m ² )/transparent vapor-deposited nylon film 1 (12 μm thick) [nylon film layer/transparent silica vapor-deposited layer]/oxygen-absorbing adhesive composition A1 (3 g/m ² )/LLDPE film 1 (40μm thickness)

[Comparative example 1]
Printing ink 1 was printed on the vapor-deposited surface of transparent vapor-deposited PET film 1 by gravure printing so that the dry coating amount was 2 g/m ² to form a printing ink layer.
Next, oxygen-absorbing adhesive A1 was applied and dried to a dry coating amount of 3 g/m ² on the printed surface, and then LLDPE film 1 was laminated by a dry lamination method and aged at 40° C. for 3 days. An oxygen-absorbing laminate having the following layer structure was obtained, and various evaluations were conducted. Layer structure: Transparent vapor-deposited PET film 1 (12 μm thick) [PET film layer/transparent alumina vapor-deposited layer]/printing ink layer (2 g/m ² )/oxygen-absorbing adhesive composition A1 (3 g/m ² )/LLDPE film 1 (40μm thickness)

[Comparative example 2]
A laminate was obtained in the same manner as in Comparative Example 1, except that transparent vapor-deposited PET film 1 was replaced with transparent vapor-deposited nylon film 1, and evaluated in the same manner.
Layer structure: Transparent vapor-deposited nylon film 1 (12 μm thick) [nylon film layer/transparent silica vapor-deposited layer]/printing ink layer (2 g/m ² )/oxygen-absorbing adhesive composition A1 (3 g/m ² )/LLDPE film 1 (40μm thickness)

<Evaluation method>
[Heat sealability]
Two laminates of 100 mm x 100 mm were cut out from the obtained laminate, stacked on top of each other with the sealant layer surfaces facing each other, and using a heat seal tester (manufactured by Tester Sangyo Co., Ltd.: TP-701-A), a laminate of 10 mm x 100 mm was cut out. The area was heat-sealed under the following conditions to prepare a peel strength test piece in which the ends were not heat-sealed or bonded and were split into two.
This test piece was cut into strips with a width of 15 mm, each end of which was split into two was attached to a tensile tester, and the peel strength (N/15 mm) was measured under the following conditions. Pass/fail judgment was made.
Heat sealing conditions Temperature: 200℃
Pressure: 1kgf/ ^cm2
Time: 1 second Test conditions Test speed: 300mm/min Load range: 50N
Pass/Fail Judgment Criteria ○: 15N/15mm or more, passed.
×: less than 15N/15mm, failing.

[Interlayer adhesion]
A strip-shaped test piece of 15 mm x 100 mm was cut out from the obtained laminate, and the adhesive strength between the layers sandwiching the oxygen-absorbing adhesive layer was measured using a tensile tester at a tensile speed of 50 mm/min. The strength was measured.
Pass/Fail Judgment Criteria ○: 3N/15mm or more, passed.
×: less than 3N/15mm, failing.

[Oxygen absorption amount]
The resulting laminate was folded in half and heat-sealed on three sides so that the inner dimensions were 130 mm x 70 mm to produce a packaging bag, and an oxygen sensor chip (Precision Sensing non-destructive oxygen sensor chip) was placed in the packaging bag. and sealed the packaging bag.
Then, 26cc of air was injected into the packaging bag using a syringe, the injection part was repaired with adhesive tape, and the oxygen concentration was measured at the time of injection and after 14 days of storage in a constant temperature bath at 25°C, and the amount of oxygen absorbed was calculated. did.

<Result summary>
The oxygen-absorbing laminate of all the embodiments of the present invention includes a printing ink layer, a printing ink component-shielding resin layer, an inorganic oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer in this order. , showed better oxygen absorption than all comparative laminates containing an inorganic oxygen barrier layer, a printing ink layer, an oxygen-absorbing adhesive layer, and a sealant layer in this order, and had excellent heat sealability, interlayer adhesion, It showed a balance of oxygen absorption.

1 Oxygen-absorbing laminate 2 Printing ink layer 2a Printing ink pattern layer 2b Printing ink solid layer 3 Printing ink component shielding resin layer 4 Inorganic oxygen barrier layer 5 Oxygen-absorbing adhesive layer 7 Sealant layer

Claims (15)

An oxygen-absorbing laminate comprising at least a printing ink layer, a printing ink component shielding resin layer, an inorganic oxygen barrier layer, an oxygen-absorbing adhesive layer, and a sealant layer in this order,
The printing ink layer contains a metal oxide pigment,
The printing ink component shielding resin layer contains one or more selected from the group consisting of nylon resin, polyolefin resin, and polyester resin,
The inorganic oxygen barrier layer contains a metal or a metal oxide,
The oxygen-absorbing adhesive layer is a layer formed from an oxygen-absorbing adhesive composition,
The oxygen-absorbing adhesive composition contains at least an oxygen-absorbing compound and an oxidation promoting catalyst,
The oxygen-absorbing compound has one or more unsaturated five-membered rings,
Any bond between the five carbon atoms constituting the unsaturated five-membered ring is a carbon-carbon double bond,
A monovalent and/or divalent or more valent electron-donating organic group 1 is bonded to the unsaturated five-membered ring,
When there is one unsaturated five-membered ring, the five-membered ring or the organic group 1 is a functional group having an active hydrogen, or the active hydrogen of the functional group having an active hydrogen is a monovalent organic group 2. has a substituted group,
When there are two or more unsaturated five-membered rings, each unsaturated five-membered ring has a divalent or higher valence that replaces the active hydrogen of the active hydrogen group on each five-membered ring or the organic group 1. An oxygen-absorbing laminate characterized by being bonded via an organic group 2. The structure of the unsaturated five-membered ring or the structure consisting of the unsaturated five-membered ring and the organic group 1 is one or two selected from the group consisting of cyclopentadiene, dicyclopentadiene, norbornene, and derivatives thereof. The oxygen-absorbing laminate according to claim 1, which is derived from the above. The oxygen-absorbing laminate according to claim 1 or 2, wherein the organic group 2 includes a structure derived from an isocyanate compound or an isocyanate compound and a hydroxyl group-containing compound. Claim 3, wherein the isocyanate compound is one or more selected from the group consisting of xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and derivatives thereof. The oxygen-absorbing laminate described above. The hydroxyl group-containing compound is selected from the group consisting of polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, phenoxy resins, and urethane chain-elongated polyols thereof. The oxygen-absorbing laminate according to claim 3 or 4, characterized in that the oxygen-absorbing laminate comprises one or more types. The oxygen-absorbing laminate according to any one of claims 1 to 5, wherein the organic group 2 does not have a crosslinkable functional group. The organic group 2 has one or more crosslinkable functional groups,
The oxygen-absorbing laminate according to any one of claims 1 to 5, wherein the crosslinkable functional group is a hydroxyl group and/or an isocyanate group. Any one of claims 1 to 5, wherein the oxygen-absorbing compound contains one or more selected from the group consisting of compounds represented by the following formulas (1) to (4). The oxygen-absorbing laminate described in .

(In the formula, each of a to e is a number of 1 or more, each of R ¹ , R ² , and R ³ is an organic group having 1 or more carbon atoms and includes at least an alkylene and/or phenylene structure, and further, One or more selected from the group consisting of polyhydric alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, phenoxy resins, and these urethane chain-extended polyols. (Can include derived structures.) The oxygen-absorbing laminate according to any one of claims 1 to 5, wherein the oxygen-absorbing compound contains a compound represented by the following formula (5).

(In the formula, f is a number of 0 or more, each of R ⁴ and R ⁵ is an organic group having 1 or more carbon atoms, an organic group containing at least an alkylene and/or phenylene structure, and a polyvalent Derived from one or more selected from the group consisting of alcohols, polyolefin polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, phenoxy resins, and these urethane chain-extended polyols structure.) The oxygen-absorbing laminate according to any one of claims 1 to 9, wherein the oxidation-promoting catalyst is a peroxide or a compound containing a cation made of a transition metal. A claim characterized in that the compound containing a cation made of a transition metal is a metal soap made of a transition metal compound capable of releasing a cation or complex made of a transition metal, and an anion or a ligand made of a fatty acid. The oxygen-absorbing laminate according to any one of Items 1 to 10. The oxygen-absorbing adhesive composition further contains a modifier,
The oxygen-absorbing laminate according to any one of claims 1 to 11, wherein the modifier contains an isocyanate compound and/or a hydroxyl group-containing compound. Claim 12, wherein the isocyanate compound is one or more selected from the group consisting of xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and derivatives thereof. The oxygen-absorbing laminate described above. The hydroxyl group-containing compound is characterized in that it contains one or more selected from the group consisting of polyester polyols, poly(meth)acrylic acid ester polyols, polyalkylene ether diols, and these urethane chain-extended polyols. The oxygen-absorbing laminate according to claim 12 or 13. An oxygen-absorbing packaging material produced using the oxygen-absorbing laminate according to any one of claims 1 to 14.

Images